Azo-dyestuffs insoluble in water and fiber dyed therewith



Patented Apr. 13, 1937 PATENT OFFICE AZO-DYESTUFFS INSOLUBLE IN WATER AND FIBER DYED THEREWITH Paul Wolff and Wilhelm Werner, Frankfort-ontlie-Mam, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application June 15, 1936, Serial No. 85,432. In Germany June 27,1935

10 Claims.

The present invention relates to azo-dyestuffs insoluble in water and to fiber dyed therewith; more particularly, it relates to compounds of the following general formula:

wherein R1 stands fora member ofthe group consisting of naphthalene and anthracene, R2 fora member of the group consisting of radicals of the benzene, naphthalene and diphenyl series, X

means alkyLY a radical of the benzene series and Z1 and Z2 stand for one of the group consisting of hydrogen and methyl.

We have found that valuable azodyestuffs insoluble in water and of various shades are obtained by coupling the diazo-compound of a 1.2- substituted 3-amino-indole with an ortho-hydroxyaryl-carboxylic acid arylide, the dyestufi components containing no groups imparting solubility as, for instance, sulfonic acid or carboxylic acid groups.

The dyestuffs may be made in the usual manner in substance, on the fiber or on any of the usual substrata adapted for the production of lakes. The dyeings obtained have a very good fastness to washing, to peroxide and to soaping and have the great advantage of yielding with acid printing pastes colored and white resist effects. The said dyestuffs may also be produced on the fiber by printing and in this case have the same good properties of fastness. r

The following examples serve to illustrate the invention, but they are not intended to limit it thereto:

50 grams of well-boiled cotton yarn are treated for /2 hour in one liter of grounding liquor, squeezed or centrifuged and dyed for hour in the developing bath,rinsed, sc aped at boiling temperature and dried.

(a) Grounding liquor tion is introduced into a bath which contains 10 cc. of sodium Turkey red oil of 50 per cent. strength and;10 cc. of caustic soda solution of 34 B. per 1000 cc. I

V (b) Developing bath 2.2 grams of 1-methyl-2-phenyl-3-amino-indole are made into a paste-with 10 grams of ace tone to which there have been added 3.1 cc. of hydrocloric acid of 20 B. and about 10 grams of ice. By addition of 0.75 gram of sodlum ni! trite the whole is diazotized belowthe surface. After about /2 hour the whole is neutralized by means of 0.75 gram of dissolved sodium carbonate and about 2 grams of sodium acetate and the solution is made up to 1000 cc.

A brown dyeing is obtained which is very fast to washing, to soaping and to peroxide, for example, to treatment with a solution containing per liter 2 grams of sodium peroxide and 6 grams of water-glass for hour at 40 C.- 0., the ratio of dyed material to liquor being 1:10. The soaping'test is carried out by boiling 2 grams of dyed material for half-an-hour with 200 cc. of water containing 1 gram of Marseille soap and 0.6 gram of calcined sodium carbonate, cooling to 40 C. within half-an-rhour, squeezing out the material between the balls of the hands 10 times by dipping it into the bath, taking it out and squeezing it, and finally rinsing it in cold water and drying it. o

The dyestufi corresponds with the following formula:

OH: OH

(lo-NHQOOH:

tained by printing with pastes containing acid salts or acids on the grounded and intermediately dried material, drying and subsequently dyeing with the diazo-solution. If the printing pastes contain diazo-compounds, colored resist eifects are obtained.

The following table indicates a number of other azo-dyestuffs obtainable according to the invention Diazo component Coupling component Tint (l) l-methyl-Z-phenyls-amino-indole.

(8) l. 5-dimethyl-2- phenyl-3-aminoindole. (9) do (13) 1 isobutyl 2 para chlorophenyl 3 a m i n o 4 6 di-methyl-indole. (14) do 17 il-m-trimeui i-apara-chlorophenyl-3-arnino-indole. 18) do.

(21 1-ethy1-2-phenyl- 3-amino-4.5-

benz-indole. (22) .do

(25) l-methyl-2-meta-xylyl-3-amino-indole.

2 .3-hydroxynaphthoyl-lamino-2.4-dimethoxy-5- chlorobenzene.

2.3-hydroxynaphthoyl-laminol-methoxybenzene.

2 .3-hydroxynaphthoyl-1- amino-4-chlorobenzene.

2' .3 -hydroxynaphthoyl-lamino-2-methyl-4-chlorobenzene.

2 .3-hyd roxynaphthoyl-lamino-2-methyl-4-methoxybenzene.

2.3'-hydroxynaphthoyl-2- amino-naphthalene.

2.3.hydroxynaphthoyl-lamino-naphthalene.

2 .3-hydroxynaphthoyl-larninol-methoxybenzene.

2 .3-hydroxynaphthoyl-laminoi-chlorobenzene.

2 .3 -hydroxynaphthoyl-lamino-2-methyl-4-chlorobenzene.

B is (2.3 -hydroxynephthoyl)-4.4-diaznino- 3.3-dimethoxydiphenyl.

2.3-hydroxy anthraoenecarboxylic acid-l-amino- Z-methylbenzene.

2 .3-h ydroxynaphthoyl-l amino-2.4-dimethoxy-5- chlorobenzene.

2.3-hydr0xynaphthoyl-1- arnino-2-methyl-4-chlorobenzene.

Y amino-2-methyl-4-methoxy-benzene.

2.3-hydroxyanthraoenecarboxylic EOid-I-HIIIlIIO-Z' methylbenzene.

2'.3-hydroxynaphthoyl-lamino-B-methyl 4 methoxybenzene.

2.3'-hydroxynaphthoyl-lamino-2-methylbenzene.

Bis-(2'.3-l1ydroxynaphthoyl)-4.4"-diamino-3.3- dimethoxy-diphenyl.

2.3-hydroxyanthracenecarboxylic acid-l-amino-2- methylbenzene 2'.3-hydroxynaphthoyl-1- amino-3-methyl-4-methoxybenzeno.

2 .3-hydroxynaphthoyl-1- amino-2-methyl-4-chlorobenzene.

2' .3-hydroxynaphthoyI-lamino-2.4-dimethoxy-5- chlorobenzene.

2. 3-hydroxyanthracenecarboxylic acid-l-amino-Z- methylbenzcne.

2.3-hydroxynaphth0yl -lamino-2.4-dimethoxy-5- chlorobenzcne.

2.3-l 1ydroxynaphthoyllam1no-3-methyl-4-methoxybenzene.

2'.3-hydroxynaphthoyl- 1- aminol-chlorobenzene.

2'.3-l1ydroxy anthracenecarboxylic acid-l-amino-2- methylbenzene.

Brown.

Brown.

Violetbrown.

R e d brown.

Brown.

Violetbrown.

D a r k r e d brown.

Reddishbrown.

Violetbrown. Currant.

Khaki.

B l u e green.

Violetdarkblue.

N a v y blue.

D a r k blue.

V i v i d green.

Violetish darkblue.

B l u e grey. Currant.

Green.

Violetish browncurrent B l u e grey.

Currant.

B 1 u e green.

Red-

brown B r o w n ish-bordeaux.

Garnet.

B I u e green.

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and a1- kalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies.

Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim:

1. The water-insoluble azo-dyestuffs of the following general formula: 5

\-C--N=N 2 g I /OH --Y N/ R1\ 10 z: I CO-NHR1 wherein R2 stands for a member of the group 5 consisting of radicals of the benzene, naphtha lene and diphenyl series, X means alkyl and Y a radical of the benzene series, yielding, when produced on. the fiber, dyeings of various shades which have good fastness properties and have the great advantage of yielding with acid printing pastes colored and white resist effects.

3. The water-insoluble azo-dyestufi of the following formula:

C-NN

CHa

yielding, when produced on the fiber, brown dyeings of very good fastness to washing, to soaping, to peroxide and of good fastness to light.

4. The water-insoluble azo-dyestuif of the following formula:

0 earn-O0 CH:

yielding, when produced on the fiber, brown dyeings of very good fastness to Washing, to soaping, to peroxide and of good fastness to light.

5. The water-insoluble azo-dyestufl of the following formula:

yielding, when produced on the fiber, violet-brown dyeings of very good :t'astness to washing, to soaping, to peroxide and of good fastness to light.

6. Fiber dyed with the azo-dyestuffs as claimed in claim 1.

'7. Fiber dyed with the azo-dyestufis as claimed in claim 2. f

8. Fiber dyed with the azo-dyestufl as claimed in claim 3.

9. Fiber dyed with the azo-dyestuff as claimed in claim 4.

10. Fiber dyed with the azo-dyestuff as claimed in claim 5.

PAUL WOLFE. WELHELM WERNER. 

